高压脉冲介质阻挡放电降解土壤中芘的研究

doi:10.11949/0438-1157.20220351

摘要/Abstract

摘要：

针对我国土壤多环芳烃的污染问题，通过自研的介质阻挡脉冲反应器处理土壤中的芘，研究了放电电压、放电频率、土壤湿度、土壤厚度、空气流速和土壤pH等条件对降解效果的影响。结果表明，随着放电电压和放电频率增加，芘的降解率提高，空气流速和土壤湿度在适宜的范围内，有利于芘的降解，增加土壤厚度和降低pH会降低芘的降解率。最适降解条件为：放电电压12.6 kV、放电频率1.0 kHz、土壤湿度3.0%、土壤厚度1 mm、空气流速2 L/min、土壤pH≥7，芘的降解率为97.04%。通过HPLC-MS和FT-IR分析，间接证明放电产生的活性物质O₃、·OH、NO _x 等导致了芘的降解，提出了芘可能的降解途径。

关键词: 等离子体, 土壤污染, 芘, 降解

Abstract:

Aiming at the pollution of the polycyclic aromatic hydrocarbons (PAHs) in soil in China, the self-developed dielectric barrier pulse reactor was used to treat pyrene in soil, and the effects of discharge voltage, discharge frequency, soil moisture, soil thickness, air velocity and soil pH on the degradation effect were studied. The results showed that the degradation rate of pyrene increased with the increase of discharge voltage and discharge frequency, and the air flow rate and soil moisture were favorable for the degradation of pyrene. The degradation rate of pyrene decreased with the increase of soil thickness and the decrease of pH. The optimal degradation conditions are as follows: discharge voltage 12.6 kV, discharge frequency 1.0 kHz, soil moisture 3.0%, soil thickness 1 mm, air flow rate 2 L/min, pH≥7. The degradation rate was 97.04%. According to the analysis of HPLC-MS and FT-IR, it was indirectly proved that the active substances such as O₃, ·OH, NO _x produced by the discharge were beneficial to the degradation of pyrene, and the possible degradation pathway of pyrene is proposed.

Key words: plasma, contaminated soil, pyrene, degradation

中图分类号:

X 53

许贤伦, 钱旸, 张兴旺, 雷乐成. 高压脉冲介质阻挡放电降解土壤中芘的研究[J]. 化工学报, 2022, 73(9): 4025-4033.

Xianlun XU, Yang QIAN, Xingwang ZHANG, Lecheng LEI. Study on treating soil contained pyrene by high voltage pulsed dielectric barrier discharge[J]. CIESC Journal, 2022, 73(9): 4025-4033.

图/表 16

图1 实验流程图

Fig.1 Flow chart of the experiments

图2 反应器示意图

Fig.2 Schematic of reactor

图3 放电电压的影响(a) 不同电压下的降解率; (b) 不同电压下的反应动力学

Fig.3 Effect of discharge voltage(a) degradation rates at different voltages; (b) kinetics at different voltages

表1 不同放电电压下芘降解动力学参数和G值

Table 1 Kinetic parameters and G values of pyrene degradation at different discharge voltages

电压/kV	k/min^-1	R²	G/（mg/kJ）
10.6	0.022	0.91	0.83
11.8	0.028	0.93	0.46
12.0	0.033	0.94	0.23
12.6	0.046	0.97	0.15
13.6	0.054	0.94	0.11

图4 放电频率的影响(a) 不同频率下的降解率; (b) 不同频率下的反应动力学; (c) 不同频率下反应器温度随时间的变化; (d) 不同温度下芘的挥发情况

Fig.4 Effect of discharge frequencies(a) degradation rates at different frequencies; (b) kinetics at different frequencies; (c) the change of temperature with time at different frequencies; (d) volatilization of pyrene at different temperatures

表2 不同放电频率下芘降解动力学参数和G值

Table 2 Kinetics parameters and G values of pyrene degradation with different frequencies

频率/kHz	k/min^-1	R²	G/(mg/kJ）
1.0	0.046	0.97	0.15
1.2	0.041	0.93	0.12
1.5	0.047	0.93	0.10
2.0	0.079	0.94	0.08

图5 土壤湿度对芘去除率的影响

Fig.5 Pyr removal efficiency with different soil moistures

图6 土壤厚度对芘去除率的影响

Fig.6 Pyr removal efficiency with different soil thickness

图7 空气流速对Pyr去除率的影响

Fig.7 Pyr removal efficiency with different air flow rate

图8 土壤pH对Pyr去除率的影响

Fig.8 Pyr removal efficiency with different soil pH

图9 处理前后高效液相色谱图

Fig.9 HPLC spectrum before and after treatment

图10 处理前后红外光谱图

Fig.10 FT-IR spectrum before and after treatment

图11 Pyr的分子结构

Fig.11 The molecular structure of Pyr

表3 Pyr分子的键长和偏原子电荷

Table 3 Main bond lengths and atomic charges of Pyr

键	键长	原子	偏原子电荷
C(1)-C(2)	1.388	C(1)	-0.097
C(2)-C(3)	1.398	C(2)	-0.162
C(3)-C(4)	1.422	C(3)	0.147
C(4)-C(5)	1.422	C(4)	-0.021
C(5)-C(6)	1.398	C(5)	0.147
C(3)-C(7)	1.432	C(6)	-0.162
C(7)-C(10)	1.355	C(7)	-0.178
C(10)-C(9)	1.432	C(8)	-0.021
C(9)-C(8)	1.422	C(9)	0.147
C(8)-C(4)	1.420	C(10)	-0.178
C(9)-C(11)	1.398	C(11)	-0.162
C(11)-C(13)	1.388	C(13)	-0.097
C(13)-C(14)	1.388	C(14)	-0.162
C(14)-C(15)	1.398	C(15)	0.147
C(15)-C(16)	1.432	C(16)	-0.178
C(16)-C(17)	1.355	C(17)	-0.178
C(17)-C(5)	1.432	H(12)	-0.102
C(11)-H(12)	1.083	H(18)	0.097
C(13)-H(25)	1.083	H(19)	0.097
C(14)-H(26)	1.083	H(20)	0.097
C(16)-H(19)	1.083	H(21)	0.106
C(17)-H(18)	1.083	H(22)	0.102
C(6)-H(23)	1.083	H(23)	0.102
C(1)-H(21)	1.083	H(24)	0.097
C(2)-H(22)	1.083	H(25)	0.106
C(7)-H(20)	1.083	H(26)	0.102
C(10)-H(24)	1.083

图12 等离子体降解芘可能的降解途径

Fig.12 Dgradation pathway of Pyr by plasma treatment

图13 降解途径中化合物的Gibbs自由能的变化（1 kcal=4.18 kJ）

Fig.13 Gibbs free energy profile of the degradation of Pyr

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